partial oxidation reactor

ABSTRACT

A reactor intended to carry out partial oxidation reactions starting from liquid feedstocks that can go from GPL to gas oil for the purpose of producing synthesis gas is characterized by finely controlled hydrodynamics and a high degree of thermal integration, and comprises an elongated jacket along an axis of any orientation, means ( 12 ) for supplying a preheated gas that contains oxygen and optionally water vapor, means ( 9 ) for supplying a hydrocarbon feedstock, means ( 11 ) for evacuation of a hydrogen-rich effluent, a first internal chamber ( 5 ) inside of which is carried out an essentially isothermal partial oxidation reaction that is connected to means ( 9 ) for supplying the hydrocarbon feedstock and to means ( 12 ) for supplying preheated gas, gas turbulizing means that are suitable for creating a perfect mixing flow, means ( 8 ) for linking first chamber ( 5 ) to a second chamber ( 7 ) with a suitable volume for carrying out a piston flow, linking means ( 8 ) that comprise at least one orifice, and second chamber ( 7 ) exchanging heat in an indirect manner over at least a portion of its length with means ( 12 ) for supplying said thus preheated gas, whereby the second chamber is connected to said means ( 11 ) for evacuating the hydrogen-rich effluent, and in which gas supply means ( 12 ) comprise an annular chamber that is essentially coaxial with the reactor jacket, and second chamber ( 7 ) is essentially coaxial with said jacket.

This application is a divisional of application Ser. No. 10/762,238,filed Jan. 23, 2004.

TECHNOLOGICAL BACKGROUND

This invention relates to the field of reactors that are intended tocarry out non-catalytic partial oxidation reactions starting from verydiverse hydrocarbon fractions for the purpose of producing a mixture ofcarbon monoxide (CO) and hydrogen (H2) that is called synthesis gas. Thereactors that are targeted by this invention are more particularlyintended for small-capacity applications as opposed to standardindustrial applications such as Fischer-Tropsch synthesis or ammoniasynthesis.

In this case, installed thermal powers of between 0.1 kW and 1000 kW areconsidered. The targeted markets are then the supply of hydrogen-richgas for fuel-cell-type (PAC) applications or hydrogen enrichment ofthermal engines.

In the text below, this type of reactor will be called a POX reactor,the usual abbreviation of partial oxidation reactions.

The use of a partial oxidation reactor for carrying out the generationof synthesis gas, and more particularly an H2-rich synthesis gas, is notoriginal in itself. By contrast, however, the technology of the reactorthat is used may be capable of novelty in a field where for low powerlevels, the majority of the players are oriented toward catalytic andnon-thermal POX concepts so as to avoid having to manage temperatureshigher than 900 or 1000° C.

In some cases, the strongly exothermic partial oxidation reactions arefollowed by endothermic vaporeforming reactions, whereby theintroduction of water vapor may take place in the form of partialoxidation reactions or in the form of vaporeforming reactions. All ofthe partial oxidation and vaporeforming reactions, when they take placesimultaneously in the same reaction chamber, are then designated underthe name of an autothermal process (ATR abbreviation).

This invention relates to the technology of the reactor forimplementation of the non-catalytic POX reactions and also applies whenthese non-catalytic POX reactions are followed by catalyticvaporeforming reactions, whereby the two types of reactions take placein separate reaction chambers.

The technology of the POX reactors has been experiencing a renewal ofinterest for several years in connection with the production of H2 forthe purpose of supplying a fuel cell (PAC). This interest for a suitablePOX reactor technology is quite often encountered within the context ofon-board reactors when the PAC is intended to provide electric energyfor the motorization of a vehicle.

Below, we are providing a general picture of recent developments in thetechnology of POX reactors in the non-catalytic domain:

In 2000, OEL-WARME Institut published two articles on the design of apartial oxidation reactor developed at the Université d'Aix la Chapelle.In this reactor, the chamber is essentially divided into two parts: afirst part termed the cold flame zone in which the hydrocarbons aremixed with preheated air so as to obtain a controlled oxidation reactionat a temperature of between 310° C. and 480° C., now called cold flame,and a second part that constitutes the core of the POX with atemperature of higher than 1000° C.

During the start-up, the hydrocarbons are vaporized in the preheated airto start up the cold flame. Then, the air temperature is lowered toobtain conditions for stabilization of the cold flame in the first partof the reactor where the temperature is kept lower than 480° C. becausebeyond this temperature, the reaction goes out of control by ignition ofthe fuel-air pre-mixture and transition from the cold-flame state to thestandard combustion state.

The adiabatic combustion temperature is then essentially reached. Thestart-up of the POX section is carried out by standard ignition. Theauthors believe that the cold flame offers a determining advantage inthat it would be responsible for the low level of soot that is observedexperimentally.

This concept may very likely lead to a limitation of the soot productionbecause of the premixing and the oxidation of heavy molecules of thefuel that are produced in the cold flame, but it imposes verysignificant limitations on the preheating temperature of the air and thefuel. Actually, beyond 480° C. in the cold flame and therefore from apreheating of the air-fuel mixture that is higher than about 350° C.,there is a risk of losing control of the reaction and a return of flameinto the cold flame chamber.

This limitation of the preheating produces a very significant economicpenalty because a large fraction of the fuel is then to be oxidized toreach the reaction temperature, which greatly penalizes the yield of thegenerator relative to a system where it would be possible to preheat theair to more than 1000° C. before the input into the combustion zone.

In the reactor concept according to the invention, it is also sought tolimit the formation of the soot but by removing the constraint on thepreheating of the air and the feedstock. To do this, it was chosen tooptimize the hydrodynamics of the reactor by dividing the reaction zonewhere the POX reaction is carried out into a first perfect-mixingreaction zone followed by a second piston reaction zone with or withouta staged injection of oxidant.

U.S. Pat. No. 3,516,807 of June 1970 of Texas Instruments refers to anintegrated POX reactor in which is carried out the preheating of airentering via the combustion effluents with the use of the fuel injectoras a Venturi tube being used to draw in the combustion air as aparticular feature. This design element of the injector is repeated inthe claims. The importance of the thermal integration on the yield isnot noted; by contrast, it is clearly indicated in the text that thereactor should operate at a temperature of 1200° C. or more to lead toreasonable dwell times, and therefore it is imperative to preheat theair that enters with the combustion gases.

Relative to this patent, this invention is based on a considerably moreadvanced thermal integration in which is considered the possibility ofreaching chamber temperatures that are higher than 1300° C. and even1500° C. to limit both the dwell times and the soot formation in thepartial oxidation chamber.

Likewise, for the reduction of soot and non-burned methane ornon-methane residues, it is very important to consider the hydrodynamicsof the POX reactor so as to carry out the combination of a firstreaction zone with an essentially isothermal perfect mixing flow and asecond reaction zone with a piston flow that is also essentiallyisothermal, at least over a portion of its length.

In a publication by P. Marty; M. Falempe; and D. Grouset entitled “TheUse of Semi-Detailed Kinetic Diagrams for a Study of the Influence ofTemperature in the Reforming of Fuels Without a Catalyst,” presented atthe Belfort Conference in November 2000, note is taken of a reactor thatis improperly called an autothermal reactor (ATR) because of the heatrecovery carried out on the combustion gases. Actually, it is possibleto derive from information contained in said publication that theconcern for thermal integration was duly taken into account by theauthor for designing a reactor that operates at a short dwell time, butthere is no information on the technology to use for optimizing thermaltransfers and heat recovery and to carry out flows so as to limit sootformation.

Patent WO 96/36836 describes a staged combustion system with integratedpreheating, i.e., a heat exchange between the combustion gases and thecombustion air. This patent essentially describes a method for reducingthe NOX that makes use of two combustion chambers.

Patents EP 0 255 748 B, EP 0 291 111 B and U.S. Pat. No. 5,653,916describe a non-catalytic POX reactor that has a burner technology thatconsists of at least 4 concentric tubes that are alternately supplied byan oxidizing gas that contains oxygen and by a hydrocarbon-rich gas. Themomentum that is necessary to the mixing is essentially created by theinjection speed of the hydrocarbon that is between 50 and 150 m/s.

Patent EP 0 380 988 B describes a partial oxidation reactor that uses aninjector that consists of 3 concentric tubes. The central tube makes itpossible to inject water vapor or CO2 at a supersonic speed at themixing point of the combustion air and the fuel.

This injection makes it possible to obtain a very quick mixing andtherefore in principle to limit the soot formation.

U.S. Pat. No. 598,297 proposes a non-catalytic POX reactor technologythat is also applicable for the POX section of ATR reactors. Theoperating temperatures are between 1000 and 1500° C. for the POX andbetween 900° C. and 1400° C. for the ATR.

A reduction of the alumina contained in the refractory materials(containing about 90% alumina) into volatile aluminum oxides wasobserved at these temperature levels that correspond to a reducingatmosphere in the reactor.

To eliminate this problem, the cited patent teaches carrying out on thewall of the reactor or behind said wall an endothermic vaporeformingreaction by circulation of a portion of the gases that have not reactedupon contact with said wall, whereby the latter was made catalytic. Thevaporeforming reaction employed makes it possible to lower the walltemperature by 100° C. to 300° C. and therefore to limit the reductionof alumina.

U.S. Pat. No. 9,732A1 relates to the integration of a POX reactor with afuel cell (PAC) of solid-oxide type (SOFC). The diagram of the processexhibits a high degree of integration between the hydrogen generator andthe SOFC cell, whereby the effluents of the cell are used to preheat thecombustion air of the POX.

A zone for recirculation of the combustion gases is located at the fuelinjection site so as to homogenize the temperatures and to limit theformation of soot. The integration of the POX with the cell itselfrequires that the POX operate at temperature levels that cannot exceed1000° C. At this temperature, the reaction times are relativelysignificant, on the order of several seconds, and there is a risk ofobtaining relatively large methane concentrations in the effluents ofthe POX.

SUMMARY DESCRIPTION OF THE INVENTION

One of the objects of the invention is to eliminate the drawbacks of theprior art. More specifically, the invention relates to a partialoxidation reactor that comprises an elongated jacket along an axis ofany orientation, means (12) for supplying a preheated gas that containsoxygen (generally air) and optionally water vapor, means (9) forsupplying a hydrocarbon feedstock, and means (11) for evacuation of ahydrogen-rich effluent, characterized in that it comprises incombination a first internal chamber (5) inside of which is carried outan essentially isothermal partial oxidation reaction that is connectedto means (9) for supplying the hydrocarbon feedstock and to means (12)for supplying preheated gas, whereby said reactor comprises gasturbulizing means that are suitable for creating a perfect mixing flowin chamber (5), means (8) for linking first chamber (5) to a secondchamber (7) of a suitable volume for carrying out a piston flow, linkingmeans (8) that comprise at least one orifice, and second chamber (7)exchanging heat in an indirect manner over at least a portion of itslength with means (12) for supplying said thus preheated gas, wherebysecond chamber (7) is connected to said evacuation means (11) of thehydrogen-rich effluent.

A perfect-mixing reactor is defined as a reactor in which a significantrecirculation of reactive fluids, in this case gaseous, is generated,before the output of the reactor, and in which the recycling rate isequal to or greater than 25% and preferably greater than 50%.

Recycling rate is generally defined as the ratio between the amount ofeffluents leaving the reactor and sent to the input of said reactor, andthe amount of fresh feedstock. When internal recirculation is required,it is necessary to imagine a flow of reagents that circulate inside thereactor, for example in the form of an internal loop, and to relate theflow of this loop to the flow of feedstock entering the reactor.

In the same way, a piston reactor is defined as a reactor in whichinternal recirculations are limited to 10% maximum, without specifying aconstraint on the axial dispersion of dwell times linked to the flowspeed.

According to a characteristic of the reactor, the gas turbulizing meansinside first chamber (5) can be selected from among the group that isformed by an internal gas recirculation ring, a baffle and a separateinjection device and essentially in countercurrent to the feedstock onthe one hand and the gas containing oxygen on the other hand.

The invention relates to the technology of a POX reactor that is usedfor carrying out a non-catalytic partial oxidation reaction, which mayor may not be followed by a vaporeforming reaction.

The partial oxidation reaction is a strongly exothermal reaction thatrequires that the reagents be made to be present in a partial oxidationchamber under suitable temperature and mixing conditions.

The reagents consist of, on the one hand, a hydrocarbon feedstock thatcan be any liquid hydrocarbon ranging from LPG (Liquefied Petroleum Gas)to heavy fuels, or else an alcohol, for example ethanol, or else an oilthat is made from biomass, such as, for example, colza oil or sunflowerseed oil, and, on the other hand, a mixture of water vapor andcombustion air. The heating of the mixture of water vapor and combustionair can be carried out by a heat exchange between said mixture and theeffluents of the reaction that are generally available at temperaturesof between 1000° C. and 1700° C.

The precise qualification of the perfect mixing or piston flows can bedone by dwell time distribution methods that rely on marking a segmentof the flow that is thus followed during its passage from the reactionzone. Qualitatively, if the dwell time distribution of the markedsegment that is observed at the output of the reaction zone is verybroad, a perfect mixing flow will be mentioned, and if, on the contrary,this distribution is very narrow, piston flow will be mentioned.

There are methods that are well known to one skilled in the art forcharacterizing specifically a given flow, and this invention is notlinked to any criterion for assessing the type of flow.

This invention is characterized by a significant and sudden change inthe flow mode in the passage from a first purely thermal reactionchamber that exhibits a perfect mixing flow nature to a second reactionchamber that exhibits a piston-flow nature, in which the reactions thatwere begun in the first reaction chamber continue, optionally completedby catalytic vaporeforming reactions.

Preferably, the first reaction chamber is adiabatic and the secondreaction chamber consists of two zones, a first zone that is alsoadiabatic, and a second zone that promotes a significant heat exchangebetween the cold gas that contains oxygen, generally air, optionallywith an addition of water vapor, and warm effluents from the reaction soas to quickly cool the latter.

The operating temperatures of the first reaction chamber and optionallythe temperature of the first zone of the second chamber are high,generally between 1100° C. and 1800° C. and preferably between 1400° C.and 1650° C., and are adjusted based on the type of feedstock.

This selection will be established based on the characteristic curves ofsoot formation so as to make the maximum move away from the criticalzone that can vary according to the nature of the feedstock,particularly based on the number of carbon atoms.

The operating pressure of the first reaction chamber will be generallybetween 1 and 20 bar absolute (1 bar=0.1 MPa) and preferably between 2and 5 bar absolute.

The amount of oxygen that is introduced preferably by the combustion airwill usually be such that the mass ratio of this amount to the amount ofstoichiometric oxygen will be between 0.1 and 0.6, and preferablybetween 0.2 and 0.4. The water vapor flow that is added to theoxygen-containing gas, generally air, will advantageously be such thatthe H2O/C molar ratio, where C represents the amount of carbon that iscontained in the feedstock, is between 0 and 2, and preferably between0.2 and 0.8.

The purpose of the first perfect-mixing reaction chamber is to carry outcombustion without a flame front, which makes it possible to limit thelocal temperatures and to operate with a homogeneous richness, creatinga significant reduction in soot formation.

Theoretically, the dwell time in this first reaction chamber should bevery high to limit the local richness and to ensure maximum recycling offree radicals. The limitation of the dwell time is provided by practicalconstraints of equipment size. A dwell time in the first perfect-mixingreaction chamber will be selected between 0.05 second and 1 second andpreferably between 0.1 second and 0.3 second.

The second piston and adiabatic reaction chamber makes it possible toeliminate the last traces of unconverted hydrocarbons, in particular thehydrocarbons such as methane, and the acetylene compounds that have beenformed in the first perfect-mixing reaction chamber. The sizing of thesecond reaction chamber with piston flow is directly linked to theoperating temperature. For a temperature of 1600° C., a dwell time of,for example, 0.05 to 0.3 second will be selected. The dwell time can beincreased if the temperature is lowered.

The dwell time in the second chamber will typically be located between0.05 second and 1 second and preferably between 0.1 second and 0.3second. This second chamber also ensures the preheating of theoxygen-containing gas to a temperature of between 800° C. and 1400° C.and preferably to a temperature of between 1000° C. and 1300° C. bymeans of an indirect heat exchange with hot effluents that are obtainedfrom the first chamber.

The second chamber is made of a ceramic-type material or a metallicmaterial that is optionally coated on the side of the hot fluid by aporous or non-porous ceramic material.

The linking between the first reaction chamber and the second reactionchamber will generally be carried out by means of an orifice that isintended to create a certain pressure drop in the passage from the firstto the second reaction chamber or by means of a porous wall or any meansthat is known to one skilled in the art such as a multiaperture plate ora honeycomb plate.

According to a characteristic of the invention, the gas supply meanscomprise an annular chamber that is essentially coaxial with the reactorjacket, whereby the second reaction chamber is also essentially coaxialwith the reactor jacket.

According to another variant, the annular chamber of the gas supplymeans surrounds the first and the second chamber, the unit formed by theannular chamber, whereby the first and the second chamber areessentially coaxial.

The sealed wall that separates the second chamber and the first chamberof the annular gas supply chamber that contains oxygen can be made of aceramic-type material that is selected from among the followingmaterials: silicon carbide, alumina, zirconia, silicon nitride ormullite.

In this case, the attachment of this wall to the outside jacket will becarried out on the cold side, i.e., the side that corresponds to theinput of the mixture of water vapor and air.

According to another variant of the invention, the wall can be made of ametallic material. In the latter case, the attachment of said wall tothe outside jacket will also be done on the cold side by means of, forexample, a flange. In all of the cases, the free expansion of the wallwill be done on the warm side, i.e., the side that corresponds to thecontact zone of the reagents.

In all of the cases, the critical point of the system is the thermalexchange zone at very high temperature that makes it possible to ensurethe preheating of the oxygen-containing gas, generally with airoptionally with a supply of water vapor, by using as a coolant theeffluent gas of the first chamber at more than 1100° C. and preferablyat more than 1400° C.

The reactor according to the invention can be used to generate ahydrogen-rich gas, whereby the effluents of the reactor are converted ina high-temperature shift stage, followed by a low-temperature shiftstage. The reaction for shifting from gas to water is called a shiftreaction, whereby the reaction consists in transforming the CO+H2Omixture into a CO2+H2 mixture.

According to certain applications that are by no means limiting, thereactor according to the invention can be used to generate a high-purityhydrogen that is intended for the supplying of a fuel cell, whereby theshift stages are optionally completed by a selective oxidation stage.

SUMMARY DESCRIPTION OF THE FIGURES

FIG. 1 shows a longitudinal cutaway view of the reactor according to theinvention in its single partial oxidation version.

FIG. 2 shows a longitudinal cutaway view of the reactor according to theinvention in its ATR version, i.e., combining a partial oxidationreaction and a vaporeforming reaction.

FIG. 3 shows a longitudinal cutaway view of the reactor according to theinvention in its single partial oxidation and double exchanger version.

FIG. 4 shows a longitudinal cutaway view of the reactor according to theinvention in its ATR and double exchanger version.

FIG. 5 shows a longitudinal cutaway view of an embodiment of the linkbetween the wall and the external jacket in the case where the wall ismade of ceramic material.

FIG. 6 shows a preferred view of the invention in which the POXcombustion chamber operates with a significant recirculation ofcombustion gases because of the internal ring that accelerates the gaseson the wall. This chamber is followed by an essentially piston andessentially adiabatic annular chamber that ensures the destruction ofresidual hydrocarbons and is equipped with a conical-type reduction thatmakes it possible to make the synthesis gas gradually converge on themetallic or ceramic tube that ensures the exchanger function. Thegradual reduction makes it possible to cool the synthesis gas beforecontact with the metallic or ceramic tube to avoid the destruction ofthe latter by excessive temperatures in the reducing environment.

DETAILED DESCRIPTION OF THE FIGURES

The device according to the invention that we will callreactor-exchanger (1) is shown in FIG. 1 that comprises an essentiallycylindrical jacket or chamber (2) with an elongated shape along axis AA′and that comprises a first hydrocarbon input (9) that is located at oneof the ends of the chamber and a second input (12) of a mixture of watervapor and air, or air that is optionally enriched with O2, located atthe other end of the chamber. We generally call this gasoxygen-containing gas to the extent that there is most often airoptionally in the presence of water vapor.

This first chamber contains a second chamber (3) that is essentiallycylindrical and coaxial to the first and forms with the first chamber ahollow internal volume (4) that makes possible the passage of themixture of water vapor and air or O2-enriched air from its input intovolume (4) by input pipe (12) to the output of said volume to supplyfirst chamber (5).

This second chamber (3) comprises an input (10) of an effluent that isformed by the mixture of input hydrocarbons and the mixture of watervapor and air or O2-enriched air that is obtained from volume (4), andan output (11) of the effluent of the partial oxidation reaction,containing an H2-rich mixture. Output (11) passes through chamber (2) ina sealed manner. Input (10) of chamber (3) is essentially aligned withinput (9) of chamber (2).

The partial oxidation reaction occurs in chamber (3), which is brokendown into two chambers:

-   -   A first reaction chamber in the direction of the flow that is        composed of a hollow internal volume (5), thermally insulated by        an adequate heat-insulated thickness (6) that is positioned        along the inside walls of chamber (5) and completed by a porous        device (8) that generates a pressure drop in the flow, whereby        this pressure drop contributes to creating a perfect-mixing        reaction chamber (5) in combination with the important        recirculation induced in the first chamber by gas reagent        turbulizing means, such as baffle (13), for example.    -   Perfect-mixing reaction chamber is defined as chamber (5) inside        which the mixture is introduced at speeds of between 10 and 100        m/s, which makes it possible to induce significant recirculation        currents, which are advantageously greater than 50% relative to        the flow that enters chamber (5) and which are somewhat        reflected by device (8).    -   A second reaction chamber (7) that is placed downstream from        chamber (5) relative to the direction of flow of the reagents        and separated from the latter by porous device (8). This second        reaction chamber (7) is designed to limit the recirculation,        less than 10% relative to the flow that enters chamber (7), so        as to carry out a piston flow. A first zone of this second        chamber can have heat-insulated walls (14) to maintain        essentially adiabatic conditions over a period of between 0 and        0.5 s.

In the second zone of chamber (7), the walls of said chamber (7) are notheat-insulated so as to promote thermal exchanges between the effluentthat is internal to said chamber (7) that contains the products of thereaction obtained from chamber (3) and the mixture of air and watervapor that circulates inside hollow volume (4) that surrounds chamber(7).

Porous device (8) can be made from any material that is resistant to thetemperatures that prevail in chamber (5) and that exhibits adequateporosity, generally created by orifices that are uniformly distributedover the entire section of the device so as to make possible linking ofchambers (5) and (7) while limiting the pressure drop to values ofbetween 10 and 500 millibar, and preferably between 10 and 100 millibar(1 millibar=10-3 bar).

The mixture of water vapor and air penetrates chamber (2) via input(12), heats by circulating along the wall of chamber (3) by heatexchange with the reaction effluents that circulate inside chambers (5)and (7), mixes with the hydrocarbon feedstock that is obtained frominput (9), and then is introduced into chamber (5) by means of input(10).

The thus constituted mixture reacts in first chamber (5) in perfectmixing flow, passes through device (8), then reacts in second chamber(7) in piston flow, and finally cools upon contact with the wall ofchamber (7) before being evacuated via output (11). The effluents ofchamber (7) essentially consist of a mixture that contains CO, H2 and N2that is called synthesis gas.

FIG. 2 shows a variant of the device according to the invention in whichthe adiabatic zone of second chamber (7) in piston flow is occupied bycatalyst for the purpose of using a vaporeforming reaction. In thiscase, the vaporeforming reaction takes place at temperatures of between1300° C. and 700° C., and preferably between 1200° C. and 900° C.

The vaporeforming catalyst can either come in the form of a bed of ballsor extrudates that completely or partially fill the volume of chamber(7) or can be placed on the walls of chamber (7), optionally after animpregnation treatment of the latter (also called a “wash coat”according to English terminology), which makes it possible to increasethe specific surface area.

The thermal energy that is necessary to the vaporeforming reaction isbrought by the reagents themselves, i.e., the effluents of the partialoxidation reaction that are obtained from chamber (5) and that penetratechamber (7) through porous system (8).

All of the reactions that take place in chamber (5) and in chamber (7)constitute a thermally balanced process called an autothermal process(ATR).

FIG. 3 represents a preferred embodiment of the invention that makes itpossible to carry out as well as possible the piston flow into secondchamber (7) and the thermal exchanges between the air and water vaporreagents, and the effluents of the partial oxidation reaction that areproduced in a portion of chamber (7).

In this embodiment of reactor-exchanger (101), found as in FIG. 1 is afirst cylindrical chamber (102) of elongated shape along an essentiallyhorizontal axis AA′, comprising an input (109) of hydrocarbons and anoutput (111) of effluents of the reaction, i.e., hydrogen-rich gas.

This first chamber (102) contains a second chamber (103) that is coaxialto the first and that forms with it a hollow internal volume of anessentially annular shape (104) that makes possible the passage ofgaseous reagents, air and water vapor, from their input into saidannular zone to their contact with the hydrocarbons that enter via pipe(109). This second chamber comprises an input (115) and an output (111)that is combined with the output that was already mentioned of firstchamber (102) because second chamber (103) is attached in a sealedmanner to first chamber (102) on the face opposite to the face thatcontains input (115).

The partial oxidation reaction occurs inside chamber (103), which isitself divided into two reaction zones.

-   -   A first reaction zone (105) that is in the direction of the        reagent flow and that consists of a hollow internal volume,        thermally insulated by a heat-insulated thickness (106) and that        has at its output (still in the direction of flow of the        reagents) an orifice with a small diameter (116) that generates        a certain pressure drop in the flow of the reagents and that is        intended to create internal recirculation movements that in        combination with the recirculation induced by baffle (13) will        impart to said first reaction zone (105) a nature that is close        to a perfect mixing flow.    -   A second reaction zone (113) of an essentially annular shape,        constituted by the space that is defined by the inside wall of        second chamber (103) and the outside wall of a third chamber        (110). This third chamber (110) with an elongated shape along        axis AA′ and that is essentially coaxial with chambers (102) and        (103) comprises an input (112) of the mixture of air and water        vapor reagents that in a sealed manner passes through first        chamber (102) and consequently also second chamber (103), since        these two chambers have a common face that is specifically the        face that is traversed by input (112).

Chamber (110) is linked to annular volume (104) via an output (117) thatis preferably located close to the common face of chambers (102) and(103). The outside walls of chamber (110) can be heat-insulated alongreaction zone (113).

By contrast, the inside walls of chamber (103) are not heat-insulatedover the entire length of reaction zone (113) specifically to promoteheat exchanges between the warm effluents that come from reaction zone(105) and that circulate inside volume (103), and the mixture of air andwater vapor that comes from input pipe (112) and that circulates insidevolume (104). The inside walls of chamber (103) can, if necessary,comprise contours intended to increase the exchange surface area.

Third chamber (110) comprises a hollow cylinder (108) that is attachedto wall (118) of said chamber, whereby this wall is the one that isparallel and the closest to the wall common to chambers (102) and (103).This hollow cylinder defines a first volume (107) that is linkeddirectly to input pipe (112).

Hollow cylinder (108) is open on its face opposite to wall (118) anddefines with the inside wall of chamber (110) a second annular volume(114) that itself is linked to annular space (104) via pipe (117). Thus,the mixture of water vapor and air penetrates chamber (107) by means ofinput pipe (112), leaves chamber (107) to enter second annular volume(114) where it is reheated upon contact with the wall of chamber (110).The mixture of water vapor and air leaves annular volume (114) viaoutput pipe (117) and penetrates first annular volume (104) where itagain reheats upon contact with the wall of reaction zone (113).

At input (115) of second chamber (103), the mixture of water vapor andair flowing through first annular volume (104) enters into contact withthe hydrocarbons that are obtained from pipe (109).

The reagents penetrate the first perfect-mixing reaction chamber (105)that they leave via orifice (116) so as to penetrate second reactionzone (113) in a piston flow, heat-insulated on its first portion toensure an adiabatic reactor function that makes it possible to oxidizethe hydrocarbons that are residual but not heat-insulated over itssecond portion to ensure cooling along the walls of chambers (103) and(110).

The reaction effluents that contain a majority of H2 and CO leave thesecond reaction zone via output pipe (111).

FIG. 4 represents another embodiment according to the invention in whichis found the configuration that was previously described and illustratedby FIG. 3, but in which second reaction chamber (113) contains avaporeforming catalyst, either in the form of a particle bed totally orpartially filling said chamber (113) or deposited in the form of acoating along the walls of chambers (103) and (110) of said zone (113).

The thus formed ATR reactor exhibits excellent thermal integration sincethese are the reagents of the vaporeforming reaction, i.e., theeffluents of the partial oxidation reaction that provide the caloriesthat are necessary to said vaporeforming reaction.

FIG. 5 shows an example of a sealed connecting system that is used toconnect internal jacket (203) to external jacket (202) in the case whereinternal jacket (203) is made of ceramic material. Internal jacket (203)is kept clamped in packing gland (205, 206, 207, or 208).

Joints (207) ensure both holding jacket (203) relative to flange (205)but also the sealing between hollow volume (211) and annular hollowvolume (212). In this way, internal jacket (203) is attached to externaljacket (202) by flange (205).

External jacket (202) is insulated thermally by a layer of insulatingmaterial (204) that can be, for example, an alumina-based textile or arefractory concrete that is not very dense.

External jacket (202) is closed by bottom (201) that makes possible theevacuation of the effluents of the reaction via pipe (213).

The connection between flange (205) and bottom (201) ensures the sealingbetween the inside and the outside of the reactor via joint (210).

FIG. 6 exhibits a preferred embodiment of reactor-exchanger (301) inwhich the perfect mixing flow is obtained by the presence of a ring inthe combustion chamber that ensures a significant recirculation of thecombustion gases.

As in the preceding cases, a first cylindrical chamber (310) that isprotected thermally inside by heat insulation (314) and that has anelongated shape along an essentially horizontal axis AA′ and thatcomprises an output (313) of effluents from the reaction, i.e., ahydrogen-rich gas, is found.

This first chamber (310) contains a second chamber of essentiallytubular shape (304) that is coaxial to the first and that forms with ita hollow internal volume (306 and 307) that makes possible the passageof the effluents of the reaction. This second chamber comprises an input(312) of gaseous reagents, air and water vapor, and is connected in asealed way to said first chamber (310).

Second chamber (304) contains a third chamber that has an essentiallytubular shape (302) that is coaxial to the second and that forms with itan essentially annular hollow internal volume (303) that makes possiblethe passage of gaseous reagents, air and water vapor, from their inputinto said annular zone until their contact with the hydrocarbons atchamber (305).

Third chamber (302) that can be heat-insulated as in FIG. 6 comprises aninput (311) of hydrocarbons and emerges in reaction chamber (305).

The partial oxidation reaction occurs inside chamber (310) that isitself divided into two reaction chambers and a heat exchange zone:

-   -   A first reaction chamber (305) that consists of a hollow        internal volume of essentially toric shape and that comprises a        toric insert (308) so as to generate a significant recirculation        of the combustion gases and to impart to said first chamber        (305) a nature that is close to a perfect mixing flow.    -   A second reaction chamber (306) of an essentially annular shape        that consists of the space that is defined by the heat-insulated        inside wall of first chamber (310) and the outside wall that is        also heat-insulated of second chamber (304).    -   The hollow volume that is thus formed is therefore entirely        heat-insulated so as to obtain an essentially adiabatic chamber        with a piston flow that ensures the destruction of residual        hydrocarbons.    -   This second chamber (306) is connected to first chamber (305) by        several holes (309), the number and the diameter of which are        defined so as to obtain a pressure drop that is adequate for        this location such that at least 50% of the combustion gases        that circulate in first chamber (305) recirculate there in the        meaning previously given in the term recirculation levels.    -   A third heat exchange zone (307) that also consists of the space        that is defined by the heat-insulated inside wall of first        chamber (310) and the outside wall of second chamber (304) on        which the thickness of the heat insulation varies according to        the distance traveled by the effluents of the reaction so as to        gradually make said effluents converge on the walls of chamber        (304) that ensures the exchanger function.

This gradual reduction in thickness makes it possible to cool thesynthesis gas before contact with the metallic or ceramic tubularchamber (304) to prevent the destruction of said chamber by excessivetemperatures in the reducing environment.

Thus, in this embodiment and contrary to preceding cases, the mixture ofwater vapor and air circulates in internal chamber (304) and theeffluents that are produced by the reaction circulate in the externalchamber.

The mixture of water vapor and air penetrates chamber (304) by input(312), reheats by circulating along the inside wall of chamber (304) byheat exchange with the reaction effluents that circulate betweenchambers (310) and (304), and mixes with the hydrocarbon feedstock thatis obtained from chamber (302) in first reaction zone (305).

Said mixture reacts in first perfect-mixing reaction chamber (305) thenpenetrates second piston reaction chamber (306) via holes (309). Thethus formed reaction effluents cool in exchange zone (307) upon contactwith the wall of chamber (304) and then are evacuated via output (313).

EXAMPLE 1 For Comparison

The example for comparison below makes it possible to compare on atypical partial oxidation feedstock the performance levels of atraditional POX reactor, i.e., operating at a relatively low temperaturewith fairly loose thermal integration, with those of a reactor-exchangeraccording to the invention.

The synthesis gas that is produced contains an H2+CO mixture that can besent as is to an SOFC cell if the initial feedstock is low in sulfur.

The H2 that is thus obtained is used for the supply of asolid-oxide-type fuel cell (SOFC) with a power of 10 kW.

A traditional POX reactor that has a 13-liter reaction zone volume issupplied by a butane feedstock and a mixture of water vapor and air.

The butane is preheated in an external exchanger at 450° C. by using theeffluents of the partial oxidation reaction as hot fluid.

The preheating temperature is set at 450° C. to limit the cracking risksof the fuel and to make possible the use of a standard effluentfeedstock exchanger. The water vapor flow rate is limited to increasethe efficiency of the reactor while limiting the soot formation. TheH2O/C molar ratio is therefore set at 0.2.

The air flow rate is fixed to reach 1200° C. in the reactor, and itcorresponds to an injected air/stoichiometric air ratio of 0.358.

The preheating temperature of the air and the water vapor is set at 450°C. This preheating is carried out with an external exchanger that usesthe heat of the effluents of the POX reaction.

The overall dwell time in the reaction zone (perfect mixing chamber plusa piston-flow chamber) is 1 second.

With such sizing, the calculations made by means of Chemkin and PROIIcommercial software show that the efficiency of the reactor is 44%.

This efficiency is defined as the ratio of the PCI of the effluent ofthe POX reaction multiplied by the H2 flow rate that is produced to thePCI of the entering feedstock multiplied by the flow rate of enteringfeedstock.

The total hydrocarbon yield is 13%, of which 9% is methane.

The amount of soot at the output of the reactor is 0.2% by weight.

EXAMPLE 2 According to the Invention

A reactor-exchanger according to FIG. 6 of this invention is supplied bythe same amounts of butane, on the one hand, and by a mixture of air andwater vapor, on the other hand. The butane is preheated to 450° C. inthe same external exchanger as in the preceding example.

The H2O/C molar ratio is set as in the preceding example at 0.2.

The temperature for preheating the air and the water vapor results froma heat exchange with the effluents of the reaction zone according to thediagram of FIG. 6.

The flow rate of air entering via pipe (312) is set so as to reach atemperature of 1600° C. in first reaction chamber (305), and the ratiobetween the flow rate of entering air and the flow rate ofstoichiometric air is 0.34.

While the heat exchange between the effluents of the reaction and themixture of air and water vapor has taken place over the entire path(304), (305), (306) and (307), the air-water vapor mixture arrives infirst chamber (305) at a temperature of 1250° C.

The overall dwell time in the first reaction chamber is 0.8 second, andthe dwell time in the second reaction chamber is 0.2 second.

A ring (308) combined with the narrowing of chamber (305) upon thearrival of the feedstock promotes the recirculation of the feedstock andeffluents in the first chamber.

The recirculation rate is about 80%.

The calculations made on the Chemkin and PROII software provide anefficiency of the reactor, which is calculated in the same way as above,of 71%.

The total hydrocarbon yield (methane included) is very low, or less than0.5%. The amount of soot at the output of the reactor is 100 ppm (partby weight per million).

These excellent results can be attributed to the combined effect ofhydrodynamics that ensure a first perfect mixing adiabatic chamber and asecond piston adiabatic chamber, combined with an increase intemperature in the first reaction chamber, which is itself made possibleby a higher level of preheating of the mixture of air and water vapor.

The increase in temperature in the first reaction chamber makes itpossible to operate in combustion without a flame front and tocontribute directly to the reduction in the amount of soot formed.

In addition, contrary to the case according to the state of the art, thedwell time in the reaction zone, and more particularly in the secondreaction chamber that is the object of heat exchanges, could besignificantly reduced without a major effect on the formation of sootand the yield of methane, which would be reflected by a reduction in thebulkiness of the reactor.

For example, if a dwell time of the first and second chamber that isreduced to 0.2 second relative to the overall dwell time of 1 secondcorresponding to the example is considered, the reaction volume wouldtherefore be reduced by a factor of 5. The efficiency of the reactorwould remain unchanged, since this efficiency essentially results fromthe temperature level that is attained in the first chamber.

The hydrocarbon yield would remain less than 0.5% and the amount of sootat the outlet of the reactor would be slightly increased to pass to 150ppm, because of the lower oxidation of the latter.

1. A process for the production of a hydrogen-rich effluent from ahydrocarbon feedstock, an alcohol, or an oil made from biomass, saidprocess comprising reacting said feedstock, alcohol, or oil in a partialoxidation reactor, said reactor comprising an elongated jacket, a firstinternal chamber (5), a second chamber (7), means (8) for linking saidfirst chamber (5) to a second chamber (7), means (12) for supplying apreheated gas, means (9) for supplying a hydrocarbon feedstock, analcohol, or an oil made from biomass, and means (11) for evacuation of ahydrogen-rich effluent connected to said second chamber (7), saidprocess comprising: supplying a preheated gas containing oxygen andoptionally water vapor to said first chamber (5) via said means (12) forsupplying a preheated, supplying a hydrocarbon feedstock, an alcohol, oran oil made from biomass to said first chamber (5) via said means (9)for supplying a hydrocarbon feedstock, an alcohol, or an oil made frombiomass, performing an essentially isothermal partial oxidation reactionin said first internal chamber (5), removing effluent form said firstchamber (5) and introducing into said second chamber via said means (8)for linking said first chamber (5) to said second chamber (7), whereinsaid second chamber has a volume suitable for carrying out a pistonflow, said linking means (8) comprises at least one orifice, and saidfirst chamber (5) and said second chamber (7) indirectly exchange heatover at least a portion of their length with said means (12) forsupplying preheated gas, evacuating hydrogen-rich effluent from saidsecond chamber (7) via said means (11) for evacuation of a hydrogen-richeffluent, wherein gas turbulizing means are provided within said firstchamber (5), said means (12) for supplying preheated gas comprises anannular chamber that is essentially coaxial with said jacket, and saidsecond chamber (7) is essentially coaxial with said jacket and comprisesa first essentially adiabatic zone that is linked to linking means (8)and a second zone that exchanges heat with said means (12) for supplyingpreheated gas.
 2. (canceled)
 3. A process according to claim 1, whereinsaid first zone of second chamber (7) contains a vaporeforming catalyst.4. A process according to claim 1, wherein said second chamber is madeof a ceramic-type material or a metallic material that is optionallycoated on the side of the hot fluid by a porous or non-porous ceramicmaterial.
 5. A process according to claim 1, wherein said gasturbulizing means inside said first chamber (5) is an internal gasrecirculation ring, a baffle, or a separate injection device that isessentially in countercurrent to the feedstock, on the one hand, and theoxygen-containing gas, on the other hand.
 6. A process according toclaim 1, wherein said first chamber (5) and said second chamber (7) areessentially coaxial with said jacket, and said means (12) for supplyingpreheated gas comprises an annular chamber which surrounds first chamber(5) and said second chamber (7).
 7. (canceled)
 8. A process according toclaim 1, in which the gas that contains the oxygen is a mass ratiorelative to the stoichiometric oxygen of between 0.1 and 0.6 and inwhich the recycling rate in the first chamber is at least equal to 25%.9. A process according to claim 1, in which said gas is preheated to atemperature of between 800° C. and 1400° C. by indirect heat exchangewith the effluent that circulates in the second chamber.
 10. A processaccording to claim 1, in which the temperature of the first chamber andoptionally the temperature of the first zone of the second chamber arebetween 1100° C. and 1800° C.
 11. A process according to claim 1, inwhich the H₂O/C molar ratio in which C designates the amount of carboncontained in the hydrocarbon feedstock is between 0 and
 2. 12. A processaccording to claim 1, in which cold ignition is carried out by injectinga gaseous hydrocarbon into the oxygen-containing gas supply and bycarrying out the ignition of the mixture that is obtained upstream fromthe first chamber.
 13. A process according to claim 1, in which thedwell times in the first chamber and in the second chamber are between50 ms and 1 second.
 14. A process according to claim 1, wherein saidrecycling rate is greater than 50%.
 15. A process according to claim 10,wherein said temperature are between 1400 and 1650° C.
 16. A processaccording to claim 11 wherein the H₂O/C molar ratio is between 0.2 and0.8.
 17. A process according to claim 3, wherein said gas turbulizingmeans inside said first chamber (5) is an internal gas recirculationring, a baffle, or a separate injection device that is essentially incountercurrent to the feedstock, on the one hand, and theoxygen-containing gas, on the other hand.
 18. A process according toclaim 5, wherein said first chamber (5) and said second chamber (7) areessentially coaxial with said jacket, and said means (12) for supplyingpreheated gas comprises an annular chamber which surrounds said firstchamber (5) and said second chamber (7).
 19. A process according toclaim 1, wherein said first chamber (5) has a hollow internal volume inwhich said gas turbulizing means is positioned, and said first chamber(5) is thermally insulated by an adequate heat-insulated thickness (6)positioned along the inside walls of said first chamber (5), and saidsecond chamber (7) comprises a first essentially adiabatic zone that islinked to linking means (8) and a second zone that exchanges heat withsaid means (12) for supplying preheated gas.
 20. A process according toclaim 19, wherein said first zone of second chamber (7) contains avaporeforming catalyst.
 21. A process according to claim 1, wherein saidfirst chamber has a hollow internal volume in which said gas turbulizingmeans is positioned, and said first chamber is thermally insulated by anadequate heat-insulated thickness positioned along the inside walls ofsaid first chamber, and said second chamber containing a third internalchamber (110) which forms an essentially annular reaction zoneconstituted by the space defined by the inside wall of said secondchamber and the outside wall of said third chamber, and said thirdchamber (110) being linked to said annular chamber of said means forsupplying heated gas, and said third chamber (110) comprising a hollowcylinder (108) that is attached to wall (118) of said third chamber,said hollow cylinder defining a first volume (107) linked directly toinput pipe (112) for delivering gas to be preheated, whereby gas to bepreheated flows from said input pipe, through said hollow chamber,through said third chamber, and into said annular chamber of said meansfor supplying heated gas.
 22. A process according to claim 21, whereinsaid annular reaction zone of said second chamber contains avaporeforming catalyst.
 23. A process for the production of ahydrogen-rich effluent from a hydrocarbon feedstock, an alcohol, or anoil made from biomass, said process comprising reacting said feedstock,alcohol, or oil in a partial oxidation reactor, said reactor comprising:a first elongated chamber along an axis of any orientation comprising afirst input for delivering a hydrocarbon feedstock, an alcohol, or anoil made from biomass, and a second input for delivering oxygencontaining gas, a second chamber positioned within said first chamber,wherein said first chamber and said second chamber form a passage, whichpassage is connected to said second input for delivering oxygencontaining gas, said second chamber (3) having an input for introducinga mixture of said hydrocarbon feedstock and said oxygen containing gas,and an output (11) for discharging partial oxidation reaction effluent,said input of said second chamber being in fluid communication with saidpassage and said first input, said second chamber further comprising afirst reaction chamber, a second reaction chamber, and a porousstructure connecting said first reaction chamber and said secondreaction chamber, said first reaction chamber having a hollow internalvolume (5) and a gas turbulizing apparatus comprising baffles withinsaid hollow volume, said first reaction chamber being in fluidcommunication with said input of said second chamber, and said secondreaction chamber being positioned downstream from said first reactionchamber and separated from said first reaction chamber by said porousstructure, said second reaction chamber being in fluid communicationwith said output of said second chamber, and wherein said passagecomprises an annular chamber, formed between said first chamber and saidsecond reaction chamber (7), and said annular chamber is essentiallycoaxial with said first chamber; said process comprising: supplying ahydrocarbon feedstock, an alcohol, or an oil made from biomass to saidfirst reaction chamber via said first input for delivering a hydrocarbonfeedstock, an alcohol, or an oil made from biomass, supplying apreheated gas containing oxygen and optionally water vapor to said firstreaction chamber via said passage and second input for delivering oxygencontaining gas, performing an essentially isothermal partial oxidationreaction in said first reaction chamber, removing effluent form saidfirst reaction chamber and introducing the effluent into said secondchamber via input for introducing a mixture of said hydrocarbonfeedstock and said oxygen containing gas, and evacuating hydrogen-richeffluent from said second chamber via said output for dischargingpartial oxidation reaction effluent.
 24. A process according to claim23, wherein said second reaction chamber comprises a first essentiallyadiabatic zone and a second zone that is in indirect heat exchange withsaid passage, wherein said first zone of said second reaction chambercontains a vapor-reforming catalyst.